Pesticidal substituted 2-[6-(pyrimidinyl)-indol-1-yl]-acrylic esters

ABSTRACT

Insecticidal and fungicidal substituted 2-[6-(pyrimidinyl)-indol-1-yl]-acrylic esters of the formula ##STR1## in which R 1  represents alkyl, or represents optionally substituted aralkyl, 
     R 2  represents dialkylamino, alkoxy or alkylthio, or represents in each case optionally substituted aralkyloxy or arylalkylthio, 
     R 3  and R 4  in each case independently of one another represent hydrogen, cyano, halogen or alkyl, 
     R 5 , R 6  and R 8  represent hydrogen or other radicals, and 
     R 7  represents optionally substituted pyrimidinyl. The corresponding acetic acid esters are also active.

This is a division of application Ser. No. 07/643,390, filed Jan. 18,1991 U.S. Pat. No. 5,182,286.

The invention relates to new substituted2-[6-(pyrimidinyl)-indol-1-yl]-acrylic esters, to new intermediates anda plurality of processes for their preparation, and to their use aspesticides.

It is known that certain substituted acrylic esters, such as, forexample, the compound methyl 3-methoxy-2-(2-methylphenyl)acrylate, havefungicidal properties (cf., for example, EP-A 178,826).

It is furthermore known that certain alkoxyacrylic esters which aresubstituted in the 2-position by a 1-indolyl radical, such as, forexample, the compound methyl 3-methoxy-2-(indol-1-yl)-acrylate, havefungicidal activity (cf. EP-A 274,825).

However, the activity of these previously known compounds is notentirely satisfactory in all fields of application, in particular whenlow amounts and concentrations are applied.

New substituted 2-[6-(pyrimidinyl)-indol-1-yl]-acrylic esters of thegeneral formula (I) have been found ##STR2## in which R¹ representsalkyl, or represents optionally substituted aralkyl,

R² represents dialkylamino, alkoxy or alkylthio, or represents in eachcase optionally substituted aralkyloxy or arylalkylthio,

R³ and R⁴ in each case independently of one another represent hydrogen,cyano, halogen or alkyl,

R⁵, R⁶ and R⁸ independently of one another in each case representhydrogen, halogen, cyano, nitro, alkyl, alkoxy, alkylthio,halogenoalkyl, halogenoalkoxy, halogenoalkylthio, alkoxycarbonyl,alkoximinoalkyl or cycloalkyl, or represent in each case optionallysubstituted aryl, aralkyl, aryloxy or arylthio, or in each caseoptionally substituted hetaryl, hetarylalkyl, hetaryloxy or hetarylthio,or

R⁵ and R⁶ together represent alkylidenedioxy or alkanediyl, and

R⁷ represents one of the following groups ##STR3## in which R⁹, R¹⁰ andR¹¹ independently of one another in each case represent hydrogen,halogen, cyano, nitro, alkyl, alkoxy, alkylthio, halogenoalkyl,alkoxycarbonyl, (di)alkylamino or (di)alkylaminocarbonyl, or representin each case optionally substituted aryl, aralkyl, aryloxy, arylthio,aralkyloxy, aralkylthio, hetaryl, hetaryloxy or hetarylthio, or

two adjacent substituents R⁹ and R¹⁰, or R¹⁰ and R¹¹, or R⁹ and R¹¹,together represent alkanediyl.

The compounds of the formula (I) can be present as geometric isomers ormixtures of isomers of various compositions. The invention extends tothe pure isomers as well as the mixtures of isomers.

Furthermore, it has been found that the new substituted2-[6-(pyrimidinyl)-indol-1-yl]-acrylic esters of the general formula (I)##STR4## in which R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ have theabovementioned meanings,

are obtained by one of the processes described below:

a) substituted 2-[6-(pyrimidinyl)-indol-1-yl]-acrylic esters of thegeneral formula (Ia) ##STR5## in which R¹, R³, R⁴, R⁵, R⁶, R⁷ and R⁸have the abovementioned meanings and

R²⁻¹ represents alkoxy or unsubstituted or substituted aralkyloxy,

are obtained when hydroxyacrylic esters or alkali metal salts thereof ofthe formula (II) ##STR6## in which M represents hydrogen, or representsan alkali metal cation, and

R¹, R³, R⁴, R⁵, R⁶, R⁷ and R⁸ have the abovementioned meanings,

are reacted with alkylating agents of the formula (III)

    R.sup.12 --E.sup.1                                         (III)

in which

R¹² represents alkyl or unsubstituted or substituted aralkyl, and

E¹ represents an electron-attracting leaving group,

if appropriate in the presence of a diluent and if appropriate in thepresence of a reaction auxiliary;

b) substituted 2-[6-(pyrimidinyl)-indol-1-yl]-acrylic esters of thegeneral formula (Ib) ##STR7## in which R¹, R³, R⁴, R⁵, R⁶, R⁷ and R⁸have the abovementioned meanings and,

R²⁻² represents dialkylamino, are obtained when substituted aceticesters of the formula (IV) ##STR8## in which R¹, R³, R⁴, R⁵, R⁶, R⁷ andR⁸ have the abovementioned meanings,

are reacted with formamides of the formula (Va) ##STR9## in which R²⁻²has the abovementioned meaning, or with formamide derivatives of theformula (Vb) ##STR10## in which R¹³ and R¹⁴ independently of one anotherrepresent alkoxy or dialkylamino and

R²⁻² has the abovementioned meaning, if appropriate in the presence of adiluent;

c) substituted 2-[6-(pyrimidinyl)-indol-1-yl]-acrylic esters of theformula (Ic) ##STR11## in which R¹, R³, R⁴, R⁵, R⁶, R⁷ and R⁸ have theabovementioned meanings and

R²⁻³ represents alkylthio or unsubstituted or substituted aralkylthio,

are obtained when ketocarboxylic acid derivatives of the formula (VI)##STR12## in which R¹, R³, R⁴, R⁵, R⁶, R⁷ and R⁸ have the abovementionedmeanings,

are reacted with organometallic compounds of the formula (VII) ##STR13##in which R²⁻³ has the abovementioned meaning, if appropriate in thepresence of a diluent;

d) substituted 2-[6-(pyrimidinyl)-indol-1-yl]-acrylic esters of theformula (Ic) are furthermore obtained when substituted acrylic esters ofthe formula (VIII) ##STR14## in which R¹, R³, R⁴, R⁵, R⁶, R⁷ and R⁸ havethe abovementioned meanings and

E² represents an electron-attracting leaving group, are reacted withthiols of the formula (IX)

    R.sup.2-3 --H                                              (IX)

in which

R²⁻³ has the abovementioned meaning, if appropriate in the presence of adiluent and if appropriate in the presence of a reaction auxiliary.

Finally, it has been found that the new substituted2-[6-(pyrimidinyl)-indol-1-yl]-acrylic esters of the general formula (I)have a good action against agricultural pests.

Surprisingly, the substituted 2-[6-(pyrimidinyl)-indol-1-yl]-acrylicesters of the general formula (I) according to the invention have aninsecticidal action as well as a considerably better fungicidal activitythan the acrylic esters which are known from the prior art and which arecompounds of a similar structure and type of action, such as, forexample, the compound methyl 3-methoxy-2-(2-methylphenyl)-acrylate.

Preferred substituents or ranges of the radicals listed in the formulaementioned above and below are illustrated below:

Alkyl in the definitions of R¹, R³, R⁴, R⁵, R⁶, R⁸, R⁹, R¹⁰ and R¹¹ inthe general formulae represents straight-chain or branched alkyl havingpreferably 1 to 8, particularly preferably 1 to 6, and in particular 1to 4, carbon atoms. Examples which may be mentioned are methyl, ethyl,n-propyl, i-propyl, n-butyl, sec-butyl, i-butyl, t-butyl, n-pentyl,i-pentyl, t-pentyl and n-hexyl.

Dialkylamino in the definition of R² or in compositions such asdialkylaminocarbonyl in the definition of R⁹, R¹⁰ and R¹¹ represents anamino group having two alkyl groups, each of which can be straight-chainor branched and identical or different, and each of which preferablycontains 1 to 6, in particular 1 to 4, carbon atoms, methyl, ethyl andn- and i-propyl being mentioned.

Examples which may be listed are dimethylamino, diethylamino,di-n-propylamino and di-i-propylamino.

The term unsubstituted or substituted aryl in the definition of R⁵, R⁶,R⁸, R⁹, R¹⁰ and R¹¹ in the general formulae is understood as meaningaryl having preferably 6 to 10 carbon atoms in the aryl moiety.Preferred examples which may be mentioned are unsubstituted orsubstituted phenyl or naphthyl, in particular phenyl.

Unsubstituted or substituted aralkyl in the definitions R¹, R⁵, R⁶, R⁸,R⁹, R¹⁰ and R¹¹ contains preferably 1 to 6, in particular 1 to 4, carbonatoms in the straight-chain or branched alkyl moiety and preferablyphenyl as the aryl moiety. Aralkyl groups which may preferably bementioned as examples are benzyl and phenethyl.

Heteroaryl in the definition of R⁵, R⁶, R⁸, R⁹, R¹⁰ and R¹¹ generallyrepresents a 5- or 6-membered ring which contains one to four,preferably one to three, identical or different hetero atoms. Heteroatoms which may preferably be mentioned are oxygen, sulphur andnitrogen; the following may preferably be mentioned as examples:pyrimidinyl, pyrrolyl, isothiazolyl, oxazolyl, pyridyl, thienyl, furyl,pyridazinyl, pyrazinyl, isoxazolyl, thiazolyl and pyrazolyl.

The term alkoxy in the definition of R², R⁵, R⁶, R⁸, R⁹, R¹⁰ and R¹¹ inthe general formulae is understood as meaning straight-chain or branchedalkoxy having preferably 1 to 6, in particular 1 to 4, carbon atoms.Examples which may be mentioned are methoxy, ethoxy, propoxy, butoxy aswell as their isomers, i-propoxy and i-, s- and t-butoxy.

Halogen in the definitions of R³, R⁴, R⁵, R⁶, R⁸, R⁹, R¹⁰ and R¹¹represents fluorine, chlorine, bromine and iodine, preferably fluorine,chlorine and bromine, and particularly preferably fluorine and chlorine.

Alkyl in radicals such as alkoximinoalkyl in the definitions of R⁵, R⁶and R⁸ represents straight-chain or branched alkyl, preferably having 1to 6, particularly preferably having 1 to 4, carbon atoms with methyl,ethyl and t-butyl being very particularly preferred. The exemplaryenumeration corresponds to that given further above.

Alkylthio in the definitions of R², R⁵, R⁶, R⁸, R⁹, R¹⁰ and R¹¹represents straight-chain or branched alkylthio having preferably 1 to 6carbon atoms, for example it is understood as meaning the followinggroups: methylthio-, ethylthio-, propylthio-, butylthio-, pentylthio aswell as their isomers, such as, for example, i-propylthio, i-, s-andt-butylthio, 1-methyl-butylthio, 2-methyl-butylthio-and3-methyl-butylthio. Preferred alkylthio radicals contain 1 to 4 carbonatoms. Methylthio, ethylthio, n-, i-, s-propylthio and n-, i-, s- andt-butylthio are particularly preferred.

Halogenoalkyl and halogenoalkoxy in the definitions of R⁵, R⁶, R⁸, R⁹,R¹⁰ and R¹¹ represent straight-chain or branched halogenoalkyl orhalogenoalkoxy each of which has 1 to 4 carbon atoms, particularlypreferably 1 or 2 carbon atoms, and in each case 1 to 9, preferably 1 to5, identical or different halogen atoms as defined under halogen; thefollowing may be mentioned by way of example: fluoromethyl,chloromethyl, bromomethyl, fluoroethyl, chloroethyl, bromomethyl,fluoro-n-propyl, chloro-n-propyl, difluoromethyl, trifluoromethyl,dichloromethyl, trichloromethyl, difluoroethyl, trifluoroethyl,trichloroethyl, chlorodifluoro-methyl, trifluorochloroethyl,chlorobutyl, fluorobutyl, fluoromethoxy, chloromethoxy, bromomethoxy,fluoroethoxy, chloroethoxy, bromoethoxy, fluoropropoxy, chloropropoxy,bromopropoxy, fluorobutoxy, chlorobutoxy, fluoro-i-propoxy,chloro-i-propoxy, difluoromethoxy, trifluoromethoxy, dichloromethoxy,trichloromethoxy, difluoroethoxy, trifluoroethoxy, tetrafluoroethoxy,trichloroethoxy, chlorodifluoromethoxy and trifluorochloroethoxy.

Halogenoalkylthio in the definitions of R⁵, R⁶ and R⁸ representsstraight-chain or branched halogenoalkylthio each of which has 1 to 4carbon atoms, particularly preferably 1 or 2 carbon atoms, and in eachcase 1 to 9, preferably 1 to 5, identical or different halogen atoms asdefined under halogen; the following may be mentioned by way of example:fluoromethylthio, chloromethylthio, bromomethylthio, fluoroethylthio,chloroethylthio, bromomethylthio, fluoropropylthio, chloropropylthio,bromopropylthio, fluorobutylthio, chlorobutylthio, bromobutylthio,fluoro-i-propylthio, chloro-i-propylthio, difluoromethylthio,trifluoromethylthio, dichloromethylthio, trichloromethylthio,difluoroethylthio, trifluoroethylthio, tetrafluoroethylthio,trichloroethylthio, chlorodifluoromethylthio andtrifluorochloroethylthio.

Alkoxycarbonyl in the definitions R⁵, R⁶, R⁸, R⁹, R¹⁰ and R¹¹ representsstraight-chain or branched alkoxycarbonyl having 1 to 4, preferably 1 or2, carbon atoms in the alkoxy radical; the following may be mentioned byway of example: methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl,i-propoxycarbonyl, n-, i-, s- and t-butoxycarbonyl.

Cycloalkyl in the definitions of R⁵, R⁶ and R⁸ represents cycloalkylhaving preferably 3 to 7, in particular 3, 5 or 6, carbon atoms.Examples which may be mentioned are unsubstituted or substitutedcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.

Unsubstituted or substituted aryloxy and arylthio in the definitions ofR⁵, R⁶, R⁸ and R⁹ in the general formulae represent aryl havingpreferably 6 to 10 carbon atoms in the aryl moiety. Examples which maybe mentioned are unsubstituted or substituted phenyl or naphthyl,phenoxy or phenylthio, in particular phenyl.

Unsubstituted or substituted aralkyloxy or aralkylthio in thedefinitions of R², R⁵, R⁶, R⁸, R⁹, R¹⁰ and R¹¹ preferably contain 1 to 6carbon atoms in the straight-chain or branched alkyl moiety andpreferably phenyl as the aryl moiety. Aralkyl groups which may bementioned by way of example are benzyl, phenethyl, benzyloxy andbenzylthio.

Hetarylalkyl, hetaryloxy and hetarylthio in the definition of R⁵, R⁶,R⁸, R⁹, R¹⁰ and R¹¹ generally represent a 5- to 6-membered ring whichcontains one or more hetero atoms, preferably 1 to 3 identical ordifferent hetero atoms. Hetero atoms which may preferably be mentionedare oxygen, sulphur and nitrogen; the following may be mentioned by wayof example: pyridyl, thienyl, furyl, pyridazinyl, pyrazinyl, isoxazolyl,thiazolyl, pyridylmethyl, thienylmethyl, furylmethyl, pyridyloxy,thienyloxy, furyloxy, pyridazinyloxy, pyrazinyloxy, isoxazolyloxy,thiazolyloxy, pyridylmethyloxy, thienylmethyloxy, furylmethyloxy,pyridylthio, thienylthio, furylthio, pyridazinylthio, pyrazinylthio,isoxazolylthio, thiazolylthio, pyridylmethylthio, thienylmethylthio andfurylmethylthio.

The substituents for the aryl radicals as such or in radicals such asarylalkyl, aryloxy, arylthio or aralkyloxy, and for the heterocyclicrings such as hetarylalkyl and hetaryl, have the meanings given below.

Halogen as a substituent generally represents fluorine, chlorine,bromine and iodine, preferably fluorine, chlorine and bromine,particularly preferably fluorine and chlorine.

Alkyl as a substituent or in radicals such as alkoximinoalkyl generallyrepresents straight-chain or branched alkyl, preferably having 1 to 6,particularly preferably 1 to 4, carbon atoms with methyl, ethyl,i-propyl and t-butyl being very particularly preferred. The exemplaryenumeration corresponds to that given further above.

Alkoxy as a substituent or in radicals such as alkoximinoalkyl generallyrepresents straight-chain or branched alkoxy having 1 to 6, particularlypreferably 1 to 3, carbon atoms per alkyl radical; preferred exampleswhich may be mentioned are: methoxy, ethoxy, n- and i-propoxy, n-, i-,s- and t-butoxy and n-hexoxy and i-hexoxy.

Alkylthio as a substituent in the radicals generally representsstraight-chain or branched alkylthio having preferably 1 to 6 carbonatoms; for example it is understood as meaning the following groups:methylthio-, ethylthio-, propylthio-, butylthio-, pentylthio as well astheir isomers, such as, for example, i-propylthio, i-, s- andt-butylthio, 1-methyl-butylthio, 2-methyl-butylthio- and3-methyl-butylthio. Preferred alkylthio radicals contain 1 to 4 carbonatoms. Methylthio, ethylthio, n-, i-, s-propylthio and n-, i-, s- andt-butylthio are particularly preferred.

Halogenoalkyl and halogenoalkoxy as substituents in the radicalsgenerally represent straight-chain or branched halogenoalkyl orhalogenoalkoxy each having 1 to 4 carbon atoms, particularly preferably1 or 2 carbon atoms, and in each case 1 to 9, preferably 1 to 5,identical or different halogen atoms as defined under halogen; thefollowing may be mentioned by way of example: fluoromethyl,chloromethyl, bromomethyl, fluoroethyl, chloroethyl, bromomethyl,fluoro-n-propyl, chloro-n-propyl, difluoromethyl, trifluoromethyl,dichloromethyl, trichloromethyl, difluoroethyl, trifluoroethyl,trichloroethyl, chloro-difluoro-methyl, trifluorochloroethyl,chlorobutyl, fluorobutyl, fluoromethoxy, chloromethoxy, bromomethoxy,fluoroethoxy, chloroethoxy, bromoethoxy, fluoropropoxy, chloropropoxy,bromopropoxy, fluorobutoxy, chlorobutoxy, fluoro-i-propoxy,chloro-i-propoxy, difluoromethoxy, trifluoromethoxy, dichloromethoxy,trichloromethoxy, difluoroethoxy, trifluoroethoxy, tetrafluoroethoxy,trichloroethoxy, chlorodifluoromethoxy and trifluorochloroethoxy.

Halogenoalkylthio as a substituent in the radicals generally representsstraight-chain or branched halogenoalkylthio in each case having 1 to 4carbon atoms, particularly preferably 1 or 2 carbon atoms, and in eachcase 1 to 9, preferably 1 to 5, identical or different halogen atoms asdefined under halogen; examples which may be mentioned are:fluoromethylthio, chloromethylthio, bromomethylthio, fluoroethylthio,chloroethylthio, bromomethylthio, fluoropropylthio, chloropropylthio,bromopropylthio, fluorobutylthio, chlorobutylthio, bromobutylthio,fluoro-i-propylthio, chloro-i-propylthio, difluoromethylthio,trifluoromethylthio, dichloromethylthio, trichloromethylthio,difluoroethylthio, trifluoroethylthio, tetrafluoroethylthio,trichloroethylthio, chlorodifluoromethylthio andtrifluorochloroethylthio.

The definitions mentioned here are also true in an analogous manner forthe preferred combinations of radicals which are listed below.

Formula (I) provides a general definition of the new substituted2-[6-(pyrimidinyl)-indol-1-yl]-acrylic esters according to theinvention. Preferred compounds of the formula (I) are those in which

R¹ represents straight-chain or branched alkyl having 1 to 6 carbonatoms, or represents benzyl,

R² represents dialkylamino having in each case 1 to 6 carbon atoms inthe individual straight-chain or branched alkyl moieties, in each casestraight-chain or branched alkoxy or alkylthio having 1 to 6 carbonatoms, or represents benzyloxy or benzylthio, each of which isoptionally monosubstituted or polysubstituted by identical or differentsubstituents, suitable phenyl substituents being: halogen, in each casestraight-chain or branched alkyl, alkoxy or alkylthio each having 1 to 4carbon atoms, in each case straight-chain or branched halogenoalkyl,halogenoalkoxy or halogenoalkylthio each having 1 to 4 carbon atoms and1 to 9 identical or different halogen atoms, or cycloalkyl having 3 to 7carbon atoms,

R³ and R⁴ in each case independently of one another represent hydrogen,cyano, fluorine, chlorine, bromine or straight-chain or branched alkylhaving 1 to 6 carbon atoms,

R⁵, R⁶ and R⁸ independently of one another in each case representhydrogen, fluorine, chlorine, bromine, cyano, nitro, in each casestraight-chain or branched alkyl, alkoxy or alkylthio each of which has1 to 4 carbon atoms, in each case straight-chain or branchedhalogenoalkyl, halogenoalkoxy or halogenoalkylthio, each of which has 1to 4 carbon atoms and 1 to 9 identical or different halogen atoms, ineach case straight-chain or branched alkoxycarbonyl or alkoximinoalkyleach of which has 1 to 4 carbon atoms in the individual alkyl moieties,cycloalkyl having 3 to 7 carbon atoms, or represent phenyl, benzyl,phenoxy, phenylthio, benzyloxy or benzylthio, each of which isunsubstituted or monosubstituted to trisubstituted in the aryl moiety byidentical or different substituents from the series comprising fluorine,chlorine, bromine, alkyl, alkoxy, alkylthio, halogenoalkyl,halogenoalkoxy or halogenoalkylthio each of which has 1 to 4 carbonatoms and if appropriate 1 to 9 identical or different halogen atoms, orrepresent pyridyl, thienyl, furyl, pyridazinyl, pyrazinyl, thiazolyl,pyridylmethyl, thienylmethyl, furylmethyl, pyridyloxy, thienyloxy,thiazolyloxy, pyridylmethyloxy, thienylmethyloxy, thienylthio,furylthio, pyridylmethylthio or thienylmethylthio each of which isoptionally monosubstituted or disubstituted in the heteroaryl moiety byidentical or different substituents from the series comprising halogen,alkyl, alkoxy, alkylthio, halogenoalkyl, halogenoalkoxy orhalogenoalkylthio each of which has 1 to 4 carbon atoms and ifappropriate 1 to 9 identical or different halogen atoms, or

R⁵ and R⁶ together represent alkanediyl having 3 to 5 carbon atoms, orrepresent alkylidenedioxy having 1 to 3 carbon atoms, and

R⁷ represents one of the following groups ##STR15## where R⁹, R¹⁰ andR¹¹ in each case independently of one another represent hydrogen,fluorine, chlorine, bromine, cyano, in each case straight-chain orbranched alkyl, alkoxy, alkylthio or halogenoalkyl having 1 to 6 carbonatoms and if appropriate 1 to 13 identical or different halogen atoms,or represent cycloalkyl having 3 to 7 carbon atoms, or representstraight-chain or branched alkoxycarbonyl having 1 to 6 carbon atoms, orrepresent dialkylaminocarbonyl, alkylaminocarbonyl, dialkylamino oralkylamino, each of which has 1 to 4 carbon atoms, each of which isstraight-chain or branched in the individual alkyl moieties and each ofwhich is optionally substituted by identical or different substituents,or represents phenyl, benzyl, phenyloxy, phenylthio, benzyloxy orbenzylthio, each of which is unsubstituted or monosubstituted totrisubstituted by identical or different substituents, or representspyrrolyl, thienyl, furyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl,pyrazolyl, imidazolyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl,triazinyl, pyrrolyloxy, thienyloxy, furyloxy, thiazolyloxy,isothiazolyloxy, oxazolyloxy, isoxazolyloxy, pyrazolyloxy,imidazolyloxy, pyridyloxy, pyrimidyloxy, pyridazinyloxy, pyrazinyloxy,pyrrolylthio, thienylthio, furylthio, thiazolylthio, isothiazolylthio,oxazolylthio, isoxazolylthio, pyrazolylthio, imidazolylthio,pyridylthio, pyrimidylthio, pyridazinylthio or pyrazinylthio, each ofwhich is unsubstituted or monosubstituted or disubstituted by identicalor different substituents, suitable substituents in each case being:halogen, in each case straight-chain or branched alkyl, alkoxy,alkylthio, halogenoalkyl, halogenoalkoxy or halogenoalkylthio each ofwhich has 1 to 4 carbon atoms and, if appropriate, in each case 1 to 9identical or different halogen atoms, alkylcarbonylamino having 1 to 4carbon atoms in the straight-chain or branched alkyl moiety,dialkylamino or dialkylaminocarbonyl each of which has 1 to 4 carbonatoms in the respective straight-chain or branched alkyl moieties, andin each case optionally substituted phenyl or benzyl, or two adjacentsubstituents R⁹ and R¹⁰, or R¹⁰ and R¹¹, or R⁹ and R¹¹, togetherrepresent alkanediyl having 3 or 4 carbon atoms.

Particularly preferred compounds of the formula (I) are those in which

R¹ represents straight-chain or branched alkyl having 1 to 4 carbonatoms,

R² represents dialkylamino having in each case 1 to 4 carbon atoms inthe respective straight-chain or branched alkyl moieties, or representsin each case straight-chain or branched alkoxy or alkylthio having 1 to4 carbon atoms, or represents benzyloxy or benzylthio,

R³ and R⁴ are identical or different and represent hydrogen, cyano,fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl or n-, i-, s-or t-butyl,

R⁵ and R⁶ are identical or different and represent hydrogen, fluorine,chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-,s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio,trifluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio,methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, ethoximinomethyl,methoximinoethyl, ethoximinoethyl, cyclopentyl or cyclohexyl, or

R⁵ and R⁶ together represent a methylenedioxy, 1,3-propanediyl or1,4-butanediyl group,

R⁷ represents one of the following groups ##STR16## where R⁹ representshydrogen, in each case straight-chain or branched alkyl, alkoxy oralkylthio each of which has 1 to 6 carbon atoms, cyclopentyl,cyclohexyl, methylamino, ethylamino, dimethylamino, diethylamino, orrepresents phenyl, benzyl, phenoxy, phenylthio, benzyloxy or benzylthioeach of which is optionally monosubstituted to trisubstituted byidentical or different substituents, or represents pyrrolyl, thienyl,furyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, pyrazolyl,imidazolyl, triazinyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl,pyridylmethyl, thienylmethyl, furylmethyl, pyridyloxy, thienyloxy,thiazolyloxy, pyridylmethyloxy, thienylmethyloxy, thienylthio,furylthio, pyridylmethylthio or thienylmethylthio each of which isoptionally monosubstituted or disubstituted by identical or differentsubstituents, suitable substituents in each case being halogen, methyl,ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- ori-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- ori-propylthio, n-, i-, s- or t-butylthio, methylcarbonylamino,ethylcarbonylamino, methylcarbonyl, ethylcarbonyl, n- ori-propylcarbonyl, n-, i-, s- or t-butylcarbonyl or halogenoalkyl,halogenoalkoxy or halogenoalkylthio each of which has 1 or 2 carbonatoms and 1 to 5 identical or different fluorine or chlorine atoms,dialkylamino or dialkylaminocarbonyl having 1 or 2 carbon atoms in theindividual alkyl moieties, or phenyl or benzyl each of which areunsubstituted or monosubstituted to disubstituted by identical ordifferent substituents, suitable phenyl or benzyl substituents in eachcase being fluorine, chlorine, methyl, methoxy or phenoxy, and

R¹⁰ and R¹¹ are identical or different and represent hydrogen,straight-chain or branched alkyl having 1 to 4 carbon atoms, chlorine,bromine, cyano, methoxycarbonyl, ethoxycarbonyl, dimethylaminocarbonyl,diethylaminocarbonyl, methylaminocarbonyl, ethylaminocarbonyl, methoxy,ethoxy, methylthio or ethylthio, or

R¹⁰ and R¹¹ together represent a methylenedioxy, 1,3-propanediyl or1,4-butanediyl group, and

R⁸ represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n-or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylthio,trifluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio,methoxycarbonyl, ethoxycarbonyl, methoximinomethyl or ethoximinomethyl.

Very particularly preferred compounds of the formula (I) are those inwhich

R¹ represents methyl or ethyl,

R² represents dimethylamino, diethylamino, methoxy, ethoxy, methylthio,ethylthio, benzyloxy or benzylthio,

R³ represents hydrogen, chlorine or methyl,

R⁴ represents hydrogen, chlorine or methyl,

R⁵ represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl,trifluoromethyl, methoxycarbonyl or ethoxycarbonyl,

R⁶ represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl,methoxy, ethoxy, methylthio, trifluoromethyl, methoxycarbonyl orethoxycarbonyl, or

R⁵ and R⁶ together represent a methylenedioxy, 1,3-propanediyl or1,4-butanediyl group,

R⁷ represents one of the following groups ##STR17## where R⁹ representshydrogen, methyl, ethyl, n- or i-propyl, n-, s-, i- or t-butyl, n- ori-amyl, n-hexyl, methoxy, ethoxy, n- or i-propoxy, methylthio,ethylthio, n- or i-propylthio, cyclohexyl, methylamino, ethylamino,dimethylamino, diethylamino, benzyl, o-, m- or p-chlorobenzyl, o-, m- orp-methylbenzyl, phenyl which is optionally monosubstituted totrisubstitited by identical or different substituents, pyridyl, thienyl,furyl, pyrimidinyl, pyridazinyl, pyrazinyl or thiazolyl, each of whichis optionally monosubstituted or disubstituted by identical or differentsubstituents, suitable substituents in each case being fluorine,chlorine, methyl, ethyl, t-butyl, methoxy, ethoxy, methylthio,methylcarbonylamino, methylcarbonyl, ethylcarbonyl, trifluoromethyl,trifluoromethoxy, trifluoromethylthio, 1,3-propanediyl, phenyl,p-chlorophenyl, m- or p-phenoxyphenyl or benzyl, and

R¹⁰ and R¹¹ independently of one another represent hydrogen, methyl,ethyl, chlorine, bromine, methoxycarbonyl or ethoxycarbonyl, or

R¹⁰ and R¹¹ together represent a methylenedioxy, 1,3-propanediyl or1,4-butanediyl group, and

R⁸ represents hydrogen, methyl or ethyl.

The following substituted 2-[6-(pyrimidinyl)-indol-1-yl]-acrylic estersof the general formula (I) may be mentioned individually in addition tothe compounds mentioned in the preparation examples: ##STR18##

                                      TABLE 1                                     __________________________________________________________________________    R.sup.1                                                                          R.sup.2                                                                             R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         R.sup.6                                                                         R.sup.7              R.sup.8                                 __________________________________________________________________________    CH.sub.3                                                                         OCH.sub.3                                                                           H H H H                                                                                                    H                                       CH.sub.3                                                                         N(CH.sub.3).sub.2                                                                   H H H H                                                                                ##STR19##           H                                       CH.sub.3                                                                         SCH.sub.3                                                                           H H H H                                                                                ##STR20##           H                                       CH.sub.3                                                                         OCH.sub.3                                                                           H H H H                                                                                ##STR21##           H                                       CH.sub.3                                                                         OCH.sub.3                                                                           H H H H                                                                                ##STR22##           H                                       CH.sub.3                                                                         OCH.sub.3                                                                           H H H H                                                                                ##STR23##           H                                       CH.sub.3                                                                         OCH.sub.3                                                                           H H H H                                                                                ##STR24##           H                                       CH.sub.3                                                                         OCH.sub.3                                                                           H H H H                                                                                ##STR25##           H                                       CH.sub.3                                                                         OCH.sub.3                                                                           H H H H                                                                                ##STR26##           H                                       CH.sub.3                                                                         OCH.sub.3                                                                           H H H H                                                                                ##STR27##           H                                       CH.sub.3                                                                         OCH.sub.3                                                                           H H H H                                                                                ##STR28##           H                                       CH.sub.3                                                                         OCH.sub.3                                                                           H H H H                                                                                ##STR29##           H                                       CH.sub.3                                                                         OCH.sub.3                                                                           H H H H                                                                                ##STR30##           H                                       CH.sub.3                                                                         OCH.sub.3                                                                           H H H H                                                                                ##STR31##           H                                       CH.sub.3                                                                         OCH.sub.3                                                                           H H H H                                                                                ##STR32##           H                                       CH.sub.3                                                                         OCH.sub.3                                                                           H H H H                                                                                ##STR33##           H                                       CH.sub.3                                                                         OCH.sub.3                                                                           H H H H                                                                                ##STR34##           H                                       CH.sub.3                                                                         OCH.sub.3                                                                           H H H H                                                                                ##STR35##           H                                       __________________________________________________________________________

If, for example, methyl3-hydroxy-2-[6-[4-(phenyl)-pyrimidin-2-yl]-indol-1-yl]-acrylate anddimethyl sulphate are used as starting substances, the course of thereaction of process (a) according to the invention may be represented bythe following equation: ##STR36##

If, for example, methyl[6-[4-(phenyl)-pyrimidin-2-yl]-indol-1-yl]-acetate and dimethylformamidedimethyl acetal are used as starting substances, the course of thereaction of process (b) according to the invention may be represented bythe following equation: ##STR37##

If, for example, methyl2-oxo-2-[6-(4-(phenyl)-pyrimidin-2-yl]-indol-1-yl]-acetate and[(methylthio)-(trimethylsilyl)]-methylene-lithium are used as startingcompounds, the course of the reaction of process (c) according to theinvention may be represented by the following equation: ##STR38##

If, for example, methyl2-[6-(4-(4-methylphenyl)-pyrimidin-2-yl]-indol-1-yl]-3-methanesulphonyloxy-acrylateand methanethiol are used as starting substances, process (d) accordingto the invention may be represented by the following equation: ##STR39##

Formula (II) provides a general definition of the hydroxyacrylic estersor their alkali metal salts which are required as starting substancesfor carrying out process (a) according to the invention. In this formula(II), R¹, R³, R⁴, R⁵, R⁶, R⁷ and R⁸ preferably represent those radicalswhich have already been mentioned in connection with the description ofthe substances of the formula (I) according to the invention as beingpreferred for these substituents.

M preferably represents hydrogen, or represents a lithium, sodium orpotassium cation.

The hydroxyacrylic esters of the formula (II) required for carrying outprocess (a) according to the invention were hitherto unknown and are asubject of the invention.

They are obtained when substituted acetic esters of the formula (IV)##STR40## in which R¹, R³, R⁴, R⁵, R⁶, R⁷ and R⁸ have the abovementionedmeanings,

are reacted with formic esters of the formula (X) ##STR41## in which R¹⁵represents alkyl, in particular methyl or ethyl, if appropriate in thepresence of a diluent such as, for example, dimethylformamide, and ifappropriate in the presence of a basic reaction auxiliary such as, forexample, sodium hydride, at temperatures of from -20° C. to +50° C.(cf., for example, EP-A 274,825).

Formic esters of the formula (X) are generally known compounds oforganic chemistry.

Formula (III) provides a general definition of the alkylating agentsfurthermore required as starting substances for carrying out process (a)according to the invention. In this formula (III), R¹² preferablyrepresents those radicals which have already been mentioned inconnection with the description of the substances of the formula (I)according to the invention as being preferred for this substituent.

E¹ represents a leaving group customary in alkylating agents, preferablyan optionally substituted alkyl, alkoxy or arylsulphonyloxy radical suchas, for example, a methoxysulphonyloxy radical, an ethoxysulphonyloxyradical or a p-toluenesulphonyloxy radical, or represents halogen, inparticular chlorine, bromine or iodine.

The alkylating agents of the formula (III) are generally known compoundsof organic chemistry.

The substituted acetic esters of the general formula (IV) which arerequired as starting substances for carrying out process (b) accordingto the invention and for the synthesis of the precursors of the formula(II) are new and likewise a subject of the invention. In this formula(IV), R¹, R³, R⁴, R⁵, R⁶, R⁷ and R⁸ preferably represent those radicalswhich have already been mentioned in connection with the description ofthe substances of the formula (I) according to the invention as beingpreferred for these substituents. The substituted acetic esters of thegeneral formula (IV) are likewise effective as plant protection agentsand are also claimed with a view to their biological use.

The compounds of the formula (IV) are obtained when indole derivativesof the general formula (XI) ##STR42## in which R³, R⁴, R⁵, R⁶, R⁷ and R⁸have the abovementioned meanings, are reacted with acetic acidderivatives of the general formula (XII)

    E.sup.3 --CH.sub.2 --COOR.sup.1                            (XII)

in which

R¹ has the abovementioned meaning and

E³ represents an electron-attracting leaving group, preferably halogen,in particular chlorine or bromine, if appropriate in the presence of adiluent such as, for example, acetonitrile or acetone, and ifappropriate in the presence of a basic auxiliary such as, for example,potassium carbonate or potassium tert.-butylate, at temperatures ofbetween -20° C. and +100° C.

The acetic acid derivatives of the formula (XII) are generally knowncompounds of organic chemistry.

The indole derivatives of the general formula (XI) were hitherto unknownand are a subject of the invention. However, they are obtained by knownprocesses in an analogous manner, for example by reacting nitrobenzenederivatives of the formula (XIII) ##STR43## in which R⁴, R⁵, R⁶, R⁷ andR⁸ have the abovementioned meanings, with compounds of the formula (XIV)##STR44## in which R³ has the abovementioned meaning,

R¹⁶ represents alkoxy or dialkylamino,

R¹⁷ represents alkoxy or dialkylamino and

R¹⁸ represents dialkylamino,

if appropriate in the presence of a diluent such as, for example,toluene or dimethylformamide, at temperatures between 25° C. and 200°C., and if appropriate under a pressure of 1 to 100 bar, to give thecompounds of the general formula (XV) ##STR45## in which R³, R⁴, R⁵, R⁶,R⁷, R⁸ and R¹⁸ have the abovementioned meanings,

and the resulting compounds of the formula (XV) may then be isolatedand/or purified and are then cyclized using customary reducing agentssuch as, for example, hydrogen, in the presence of a suitable catalystsuch as, for example, Raney nickel, and at a pressure between 1 and 200bar at temperatures between -20° C. and +200° C., if appropriate in thepresence of a diluent such as, for example, methanol, ethanol,tetrahydrofuran or dioxane, and if appropriate in the presence of aninert gas such as, for example, nitrogen.

The compounds of the formula (XV) are new and likewise a subject of theinvention.

The compounds of the general formula (XIV) are generally known compoundsof organic chemistry (cf. Tetrahedron 35, 1675 (1979)).

The nitrobenzene derivatives of the formula (XIII) ##STR46## in whichR⁴, R⁵, R⁶, R⁷ and R⁸ have the abovementioned meanings, are new.

The nitrobenzene derivatives of the formula (XIII) are obtained by oneof the processes described below:

a) Nitrobenzene derivatives of the general formula (XIII-a) ##STR47## inwhich R⁴, R⁵, R⁶, R⁸, R⁹, R¹⁰ and R¹¹ have the abovementioned meanings,

are obtained when compounds of the formula (XVI) ##STR48## in which R⁴,R⁵, R⁶ and R⁸ have the abovementioned meanings and

HX represents the equivalent of an inorganic acid such as, for example,hydrochloric acid, or of an organic acid such as, for example, oxalicacid,

are reacted with enaminones of the formula (XVII) ##STR49## in which R⁹has the abovementioned meaning and

R¹⁹ and R²⁰ are identical or different and preferably representstraight-chain or branched alkyl having 1 to 6 carbon atoms, inparticular straight-chain or branched alkyl having 1 to 4 carbon atoms,

if appropriate in the presence of a diluent such as, for example,methanol or ethanol, and if appropriate in the presence of a base suchas, for example, sodium methanolate or sodium ethanolate, attemperatures between +20° C. and +200° C.

b) Nitrobenzene derivatives of the general formula (XIII-b) ##STR50## inwhich R⁴, R⁵, R⁶, R⁸, R⁹, R¹⁰ and R¹¹ have the abovementioned meanings,

are obtained when compounds of the formula (XVIII) ##STR51## in whichR⁴, R⁵, R⁶, R⁸, R¹⁹ and R²⁰ have the abovementioned meanings,

are reacted with amidine derivatives of the formula (XIX) ##STR52## inwhich R⁹ has the abovementioned meaning and

HX represents the equivalent of an inorganic acid such as, for example,hydrochloric acid, or of an organic acid such as, for example, oxalicacid,

if appropriate in the presence of a diluent such as, for example,methanol or ethanol, and if appropriate in the presence of a base suchas, for example, sodium methanolate or sodium ethanolate, attemperatures between +20° C. and +200° C.

c) The nitrobenzene derivatives of the general formulae (XIII-c),(XIII-d) and (XIII-e) ##STR53## in which R⁴, R⁵, R⁶, R⁸, R⁹, R¹⁰ and R¹¹have the abovementioned meanings,

are obtained when nitrohalogenoaromatic compounds of the general formula(XX) ##STR54## in which R⁴, R⁵ and R⁶ have the abovementioned meaningand

Y represents halogen, preferably bromine or iodine, are reacted either

α) with boronic acids of the formula (XXI) ##STR55## in which R⁷ has theabovementioned meaning, or

β) with tin compounds of the formula (XXII)

    R.sup.7 --Sn(R.sup.21).sub.3                               (XXII)

in which

R⁷ has the abovementioned meaning and

R²¹ preferably represents straight-chain or branched alkyl having 1 to 6carbon atoms, in particular straight-chain or branched alkyl having 1 to4 carbon atoms,

in a known manner (cf. Nachr. Chem. Tech. Lab. 36, 1324 (1958) in atwo-phase reaction in the presence of a diluent such as, for example,benzene or toluene, and in the presence of a base such as, for example,aqueous sodium carbonate solution or sodium hydrogen carbonate solution,and in the presence of a catalyst such as, for example,tetrakisphenylphosphinepalladium (O), palladiumdichloride/triphenylphosphine or bis-(triphenylphosphine) palladiumdichloride, at temperatures between +20° C. and +200° C.

The compounds of the formula (XVI) and the amidine derivatives of theformula (XIX) are known and/or can be prepared in analogy to knownprocesses (cf. Houben-Weyl-Muller, "Methoden der organischen Chemie[Methods of Organic Chemistry]", vol. XI/2, p. 38 et seq., Thieme VerlagStuttgart (1958)).

Enaminones of the formula (XVII) and compounds of the formula (XVIII)are known and/or can be prepared in analogy to known processes (cf.Chem. Ber. 97, 3397 (1964)).

Boronic acids of the formula (XXI) are known and/or can be prepared inanalogy to known processes (cf. Adv. Chem. Ser. 102 (1959)).

Tin compounds of the formula (XXII) are likewise known and/or may beprepared by known processes (cf. Tetrahedron Lett. 4407 (1986)).

Formulae (Va) and (Vb) provide general definitions of the formamides andtheir derivatives furthermore required as starting substances forcarrying out process (b) according to the invention. In these formulae(Va) and (Vb), R²⁻² preferably represents dialkylamino having in eachcase 1 to 6, in particular 1 to 4, carbon atoms in the individualstraight-chain or branched alkyl moieties. R²⁻² very particularlypreferably represents dimethylamino or diethylamino.

R¹³ and R¹⁴ independently of one another preferably represent in eachcase straight-chain or branched alkoxy having 1 to 4 carbon atoms, inparticular methoxy or ethoxy, or represent a dialkylamino radical havingin each case 1 to 6, in particular 1 to 4, carbon atoms in theindividual straight-chain or branched alkyl moieties.

The formamides of the formula (Va) and their derivatives of the formula(Vb) are generally known compounds of organic chemistry.

Formula (VI) provides a general definition of the ketocarboxylic acidderivatives required as starting substances for carrying out process (c)according to the invention.

In this formula (VI), R¹, R³, R⁴, R⁵, R⁶, R⁷ and R⁸ preferably representthose radicals which have already been mentioned in connection with thedescription of the substances of the formula (I) according to theinvention as being preferred for these substituents.

The ketocarboxylic acid derivatives of the formula (VI) are new andlikewise a subject of the invention. However, they are obtained inanalogy to known processes, for example by reacting oxalic esters of theformula (XXIII) ##STR56## in which R¹ has the abovementioned meaning and

E⁴ represents alkoxy or halogen, in particular methoxy, ethoxy orchlorine,

with indole derivatives of the formula (XI) ##STR57## in which R³, R⁴,R⁵, R⁶, R⁷ and R⁸ have the abovementioned meanings, if appropriate inthe presence of a diluent such as, for example, dichloromethane ortetrahydrofuran, and if appropriate in the presence of a base such as,for example, n-butyllithium, sodium hydride, potassium t-butylate,triethylamine or pyridine, at temperatures between -80° C. and +80° C.(cf. DE-OS (German Published Specification) 3,807,232).

Formula (VII) provides a general definition of the organometalliccompounds furthermore required as starting substances for carrying outprocess (c) according to the invention. In this formula (VII), R²⁻³preferably represents those radicals which have already been mentionedin connection with the description of the substances of the formula (I)according to the invention as being preferred for this substituent.

The organometallic compounds of the formula (VII) are known (cf., forexample, J. Org. Chem. 33, 780 [1968]; J. Org. Chem. 37, 939 [1972]).

Formula (VIII) provides a general definition of the substituted acrylicesters required as starting substances for carrying out process (d)according to the invention. In this formula (VIII), R¹, R³, R⁴, R⁵, R⁶,R⁷ and R⁸ preferably represent those radicals which have already beenmentioned in connection with the description of the substances of theformula (I) according to the invention as being preferred for thesesubstituents.

E² preferably represents a suitable acyloxy or sulphonyloxy radical, inparticular an acetoxy, a methanesulphonyloxy or a p-toluenesulphonyloxyradical.

The substituted acrylic esters of the formula (VIII) were hithertounknown.

They are obtained when hydroxyacrylic esters of the formula (II)##STR58## in which M, R¹, R³, R⁴, R⁵, R⁶, R⁷ and R⁸ have theabovementioned meanings,

are reacted with acid chlorides of the formula (XXIV)

    R.sup.22 --Cl                                              (XXIV)

in which

R²² represents an acyl or sulphonyl radical, in particular an acetyl, amethanesulphonyl or a p-toluenesulphonyl radical,

if appropriate in the presence of a diluent such as, for example,dichloromethane, and if appropriate in the presence of an acid-bindingagent such as, for example, triethylamine or pyridine, at temperaturesof from -20° C. to +120° C.

Acid chlorides of the formula (XXIV) are generally known compounds oforganic chemistry.

Formula (IX) provides a general definition of the thiols furthermorerequired as starting substances for carrying out process (d) accordingto the invention. In this formula (IX), R²⁻³ preferably represents thoseradicals which have already been mentioned in connection with thedescription of the substances of the formula (I) according to theinvention as being preferred for this substituent.

The thiols of the formula (IX) are generally known compounds of organicchemistry.

Suitable diluents for carrying out process (a) according to theinvention are inert organic solvents. These include, in particular,aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbonssuch as, for example, benzine, benzene, toluene, xylene, chlorobenzene,petroleum ether, hexane, cyclohexane, dichloromethane, chloroform orcarbon tetrachloride, ethers such as diethyl ether, dioxane,tetrahydrofuran or ethylene glycol dimethyl ether or ethylene glycoldiethyl ether, nitriles such as acetonitrile or propionitrile, amidessuch as dimethylformamide, dimethylacetamide, n-methylformanilide,N-methylpyrrolidone or hexamethylphosphoric triamide, or sulphoxidessuch as dimethyl sulphoxide.

If appropriate, process (a) according to the invention can also becarried out in a two-phase system such as, for example, water/toluene orwater/dichloromethane, if appropriate in the presence of a phasetransfer catalyst. Examples of such catalysts which may be mentionedare: tetrabutylammonium iodide, tetrabutylammonium bromide,tributyl-methylphosphonium bromide, trimethyl-C₁₃ /C₁₅ -alkylammoniumchloride, dibenzyl-dimethyl-ammonium methylsulphate, dimethyl-C₁₂ /C₁₄-alkylbenzylammonium chloride, tetrabutylammonium hydroxide, 15-crown-5,18-crown-6, triethylbenzylammonium chloride, trimethylbenzylammoniumchloride or tris-[2-(2-methoxyethoxy)-ethyl]-amine.

Process (a) according to the invention is preferably carried out in thepresence of a suitable basic reaction auxiliary. Suitable reactionauxiliaries are all inorganic and organic bases which can customarily beused. The following are preferably used: alkali metal hydrides, alkalimetal hydroxides, alkali metal amides, alkali metal alcoholates, alkalimetal carbonates or alkali metal hydrogen carbonates such as, forexample, sodium hydride, sodium amide, sodium hydroxide, sodiummethylate, sodium ethylate, potassium t-butylate, sodium carbonate orsodium hydrogen carbonate, and also tertiary amines such as, forexample, triethylamine, N,N-dimethylaniline, pyridine,N,N-dimethylaminopyridine, diazabicyclooctane (DABCO),diazabicyclononene (DBN) or diazabicycloundecene (DBU).

When carrying out process (a) according to the invention, the reactiontemperatures can be varied within a substantial range. In general, theprocess is carried out at temperatures of from -30° C. to +120° C.,preferably at temperatures of from -20° C. to +60° C.

For carrying out process (a) according to the invention, 1.0 to 10.0moles, preferably 1.0 to 5.0 moles, of alkylating agent of the formula(III) and, if appropriate, 1.0 to 5.0 moles, preferably 1.0 to 2.0moles, of reaction auxiliary are generally employed per mole of3-hydroxyacrylic ester or of a corresponding alkali metal salt of theformula (II). It is also possible in this context to prepare the3-hydroxyacrylic esters or their alkali metal salts of the formula (II)which are required as starting compounds for carrying out process (a)according to the invention, directly in the reaction vessel in apreceding reaction and to further react them from the reaction mixturewith the alkylating agent of the formula (III), without isolation,according to process (a) according to the invention ("one-pot process").The reaction is carried out and the reaction products are worked up andisolated by generally customary methods (cf. also the preparationexamples).

Suitable diluents for carrying out process (b) according to theinvention are inert organic solvents. These include, in particular,aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbonssuch as, for example, benzine, benzene, toluene, xylene, chlorobenzene,petroleum ether, hexane, cyclohexane, dichloromethane, chloroform orcarbon tetrachloride, or ethers such as diethyl ether, dioxane,tetrahydrofuran or ethylene glycol dimethyl ether or ethylene glycoldiethyl ether.

However, it is also possible to carry out process (b) according to theinvention without adding a diluent.

When carrying out process (b) according to the invention, the reactiontemperatures can be varied within a substantial range. In general, theprocess is carried out at temperatures of from -20° C. to +200° C.,preferably at temperatures from 0° C. to 150° C.

For carrying out process (b) according to the invention, 1.0 to 30.0moles, preferably 1.0 to 15.0 moles, of formamide of the formula (Va) orof a corresponding derivative of the formula (Vb) are generally employedper mole of substituted acetic ester of the formula (IV).

The reaction is carried out and the reaction products are worked up andisolated by generally customary methods (cf. in this context also G.Mathieu; J. Weill-Raynal "Formation of C--C Bonds", Vol. I; p. 229-244;Thieme Verlag Stuttgart 1973).

Suitable diluents for carrying out process (c) according to theinvention are inert organic solvents. These include, in particular,aliphatic, alicyclic or aromatic hydrocarbons such as, for example,benzine, toluene, xylene, petroleum ether, hexane or cyclohexane, orethers, such as diethyl ether, dioxane, tetrahydrofuran or ethyleneglycol dimethyl ether or ethylene glycol diethyl ether.

When carrying out process (c) according to the invention, the reactiontemperatures can be varied within a substantial range. In general, theprocess is carried out at temperatures of from -100° C. to +100° C.,preferably at temperatures of from -80° C. to +50° C.

For carrying out process (c) according to the invention, 1.0 to 1.5moles, preferably 1.0 to 1.2 moles, of organometallic compound of theformula (VII) are generally employed per mole of ketocarboxylic acidderivative of the formula (VI). The reaction is carried out and thereaction products are worked up and isolated by known processes (cf.,for example, J. Org. Chem. 33, 780 [1968]; J. Org. Chem. 37, 939[1972]).

Suitable diluents for carrying out process (d) according to theinvention are inert organic solvents. These include, in particular,aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbonssuch as, for example, benzine, benzene, toluene, xylene, chlorobenzene,petroleum ether, hexane, cyclohexane, dichloromethane, chloroform orcarbon tetrachloride, ethers such as diethyl ether, dioxane,tetrahydrofuran or ethylene glycol dimethyl ether or ethylene glycoldiethyl ether, ketones such as acetone or butanone, nitriles such asacetonitrile or propionitrile, amides such as dimethylformamide,dimethylacetamide, N-methylformanilide, N-methylpyrrolidone orhexamethylphosphoric triamide, esters such as ethyl acetate, orsulphoxides such as dimethyl sulphoxide.

Process (d) according to the invention is preferably carried out in thepresence of a suitable reaction auxiliary. Suitable reaction auxiliariesare all customary inorganic or organic bases. These include, forexample, alkali metal hydroxides such as sodium hydroxide or potassiumhydroxide, alkali metal carbonates such as sodium carbonate, potassiumcarbonate or sodium hydrogen carbonate, or tertiary amines such astriethylamine, N,N-dimethylaniline, pyridine, N,N-dimethylaminopyridine,diazabicyclooctane (DABCO), diazabicyclononene (DBN) ordiazabicycloundecene (DBU).

When carrying out process (d) according to the invention, the reactiontemperatures can be varied within a substantial range. In general, theprocess is carried out at temperatures of from -20° C. to 180° C.,preferably at temperatures of from 0° C. to 150° C.

If appropriate, the process according to the invention can also becarried out under pressure, depending on the boiling point of thereactants used, for example when low-boiling thiols of the formula (IX)are employed.

In this case, it is preferred to carry out the process under thepressure which is established under the reaction conditions when themixture is heated to the reaction temperature required.

For carrying out process (d) according to the invention, 1.0 to 20.0moles, preferably 1.0 to 5.0 moles, of thiol of the formula (IX) and, ifappropriate, 1.0 to 5.0 moles, preferably 1.0 to 1.5 moles, of reactionauxiliary are generally employed per mole of substituted acrylic esterof the formula (VIII). The reaction is carried out and the reactionproducts are worked up and isolated by generally customary methods.

The active compounds of the formula (I) and of the formula (IV)according to the invention have a powerful action against pests and canbe employed in practice for combating undesired harmful organisms. Theactive compounds are suitable for use as plant protection agents, inparticular as fungicides or insecticides.

Fungicidal agents in plant protection are employed for combatingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

Some causative organisms of fungal diseases which come under the genericnames listed above may be mentioned as examples, but not by way oflimitation:

Pythium species, such as, for example, Pythium ultimum;

Phytophthora species, such as, for example, Phytophthora infestans;

Pseudoperonospora species, such as, for example, Pseudoperonosporahumuli or Pseudoperonospora cubensis;

Plasmopara species, such as, for example, Plasmopara viticola;

Peronospora species, such as, for example, Peronospora pisi or P.brassicae;

Erysiphe species, such as, for example, Erysiphe graminis;

Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;

Podosphaera species, such as, for example, Podosphaera leucotricha;

Venturia species, such as, for example, Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres or P.graminea (conidia form: Drechslera, syn: Helminthosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus(conidia form: Drechslera, syn: Helminthosporium);

Uromyces species, such as, for example, Uromyces appendiculatus;

Puccinia species, such as, for example, Puccinia recondita;

Tilletia species, such as, for example, Tilletia caries;

Ustilago species, such as, for example, Ustilago nuda or Ustilagoavenae;

Pellicularia species, such as, for example, Pellicularia sasakii;

Pyricularia species, such as, for example, Pyricularia oryzae;

Fusarium species, such as, for example, Fusarium culmorum;

Botrytis species, such as, for example, Botrytis cinerea;

Septoria species, such as, for example, Septoria nodorum;

Leptosphaeria species, such as, for example, Leptosphaeria nodorum;

Cercospora species, such as, for example, Cercospora canescens;

Alternaria species, such as, for example, Alternaria brassicae and

Pseudocercosporella species, such as, for example,

Pseudocercosporella herpotrichoides.

The good toleration, by plants, of the active compounds, at theconcentrations required for combating plant diseases, permits treatmentof above-ground parts of plants, of vegetative propagation stock andseeds, and of the soil.

In this context, the active compounds of the formulae (I) and (IV)according to the invention can be with particularly good success forprotectively combating rice blast disease (Pyricularia oryzae) andplasmopara on vines. Moreover, the active compounds according to theinvention have a very good fungicidal action against septoria nodorum,cochliobolus sativus, pyrenophora teres and fusarium nivale.

Moreover, the active compounds of the formulae (I) and (IV) according tothe invention show an additional fungicidal action against Oomycetes,Venturia species on apples, Botrytis and Pellicularia sasakii on rice,and a broad and good in-vitro action.

In addition, the active compounds of the general formula (I) aresuitable for combating animal pests, preferably arthropods andnematodes, in particular insects and arachnids, encountered inagriculture, in forestry, in the protection of stored products and ofmaterials, and in the hygiene field. They are active against normallysensitive and resistant species and against all or some stages ofdevelopment. The abovementioned pests include:

From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus. Fromthe order of the Chilopoda, for example, Geophilus carpophagus andScutigera spec. From the order of the Symphyla, for example,Scutigerella immaculata. From the order of the Thysanura, for example,Lepisma saccharina. From the order of the Collembola, for example,Onychiurus armatus. From the order of the Orthoptera, for example,Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattellagermanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoriamigratorioides, Melanoplus differentialis and Schistocerca gregaria.From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp.. Fromthe order of the Anoplura, for example, Phylloxera vastatrix, Pemphigusspp., Pediculus humanus corporis, Haematopinus spp. and Linognathus spp.From the order of the Mallophaga, for example, Trichodectes spp. andDamalinea spp.

From the order of the Thysanoptera, for example, Hercinothrips femoralisand Thrips tabaci.

From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp. From the order of the Homoptera, for example,Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphisgossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Doralispomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae,Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelisbilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae,Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii,Aspidiotus hederae, Pseudococcus spp. and Psylla spp.

From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella maculipennis, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp. Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestrabrassicae, Panolis flammea, Prodenia litura, Spodoptera spp.,Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyraustanubilalis, Ephestia kuehniella, Galleria mellonella, Tineolabisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoeciapodana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella,Homona magnanima and Tortrix viridana.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Acanthoscelides obtectus, Acanthoscelidesobtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsadecemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodeschrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilussurinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus,Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica,Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctusspp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbiumpsylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderusspp., Melolontha melolontha, Amphimallon solstitialis and Costelytrazealandica.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp. From the order ofthe Diptera, for example, Aedes spp., Anopheles spp., Culex spp.,Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleaeand Tipula paludosa.

From the order of the Siphonaptera, for example, Xenopsylla cheopis andCeratophyllus spp. From the order of the Arachnida, for example, Scorpiomaurus and Latrodectus mactans.

From the order of the Acarina, for example, Acarus siro, Argas spp.,Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptrutaoleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalommaspp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp.,Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychusspp..

The phytoparasitic nematodes include Pratylenchus spp., Radopholussimilis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heteroderaspp., Globedera ssp., Meloidogyne spp., Aphelenchoides spp., Longidorusspp., Xiphinema spp. and Trichodorus spp..

The active compounds of the formula (I) according to the invention aredistinguished by an outstanding insecticidal activity, in particularwhen employed against beetle larvae such as, for example, Phaedoncholeariae, Plutella xylostella and Spodoptera frugiperda, againstcicadas such as, for example, Nephotettix, and against aphids such as,for example, Myzus persicae, and against spider mites such as, forexample, Tetranychus urticae. The active compounds according to theinvention furthermore have a very good ovicidal action.

Depending on their particular physical and/or chemical properties, theactive compounds of the formulae (I) and (IV) can be converted to thecustomary formulations, such as solutions, emulsions, suspensions,powders, foams, pastes, granules, aerosols, natural and syntheticmaterials impregnated with active compound, very fine capsules inpolymeric substances and in coating compositions for seed, and informulations used with burning equipment, such as fumigating cartridges,fumigating cans, fumigating coils and the like, as well as ULV cold mistand warm mist formulations.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurface-active agents, that is emulsifying agents and/or dispersingagents and/or foam-forming agents. In the case of the use of water as anextender, organic solvents can, for example, also be used as auxiliarysolvents. As liquid solvents, there are suitable in the main: aromatics,such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics orchlorinated aliphatic hydrocarbons, such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulphoxide, as well as water; by liquefied gaseous extenders orcarriers are meant liquids which are gaseous at ambient temperature andunder atmospheric pressure, for example aerosol propellants, such ashalogenated hydrocarbons, as well as butane, propane, nitrogen andcarbon dioxide; as solid carriers there are suitable: for example groundnatural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly disperse silica, alumina and silicates; assolid carriers for granules there are suitable: for example crushed andfractionated natural rocks such as calcite, marble, pumice, sepioliteand dolomite, as well as synthetic granules of inorganic and organicmeals, and granules of organic material such as sawdust, coconut shells,corn cobs and tobacco stalks; as emulsifying and/or foam-forming agentsthere are suitable: for example non-ionic and anionic emulsifiers, suchas polyoxyethylene fatty acid esters, polyoxyethylene fatty alcoholethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates as well as albumin hydrolysis products; asdispersing agents there are suitable: for example lignin-sulphite wasteliquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedye-stuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain 0.1 and 95 per cent by weight ofactive compound, preferably 0.5 to 90%.

The active compounds of the formulae (I) and (IV) according to theinvention can be present in the formulations as a mixture with otherknown active compounds, such as fungicides, insecticides, acaricides andherbicides and as mixtures with fertilizers and growth regulators.

The active compounds of the formulae (I) and (IV) can be used as such orin the form of their formulations or the use forms prepared therefrom,such as ready-to-use solutions, suspensions, wettable powders, pastes,soluble powders, dusts and granules. They are used in the customarymanner, for example by watering, spraying, atomizing, scattering,dusting, foaming, brushing on and the like. It is furthermore possibleto apply the active compounds by the ultra-low volume method or toinject the active compound preparation or the active compound itselfinto the soil. The seeds of the plants can also be treated.

In the treatment of parts of plants, the active compound concentrationsin the use forms can be varied within a substantial range. They are, ingeneral, between 1 and 0.0001% by weight, preferably between 0.5 and0.001%.

In the treatment of seed, amounts of active compound of 0.001 to 50 gper kilogram of seed, preferably 0.01 to 10 g, are generally required.

In the treatment of soil, active compound concentrations of 0.00001 to0.1% by weight, preferably 0.0001 to 0.02% by weight, are required atthe place of action.

PREPARATION EXAMPLES EXAMPLE 1 ##STR59## (Process (a)) ("One-Pot"Variant)

A mixture of 8.58 g (25 mmol) of methyl[6-[4-(phenyl)-pyrimidin-2-yl]-indol-1-yl]-acetate and 28.6 ml of methylformate in 15 ml of dimethylformamide are slowly added dropwise at atemperature of 0° C. to 5° C. to a stirred and cooled suspension of 1.71g (57 mmol) of sodium hydride (80% in paraffin) in 15 ml ofdimethylformamide. Stirring at 0° C. is continued for 2 hours, and 7.5ml (79 mmol) of dimethyl sulphate are then added at the same temperatureto the vigorously stirred mixture. Stirring is continued for one hour,during which process the mixture is allowed to come to room temperature;excess saturated sodium hydrogen carbonate solution is then added to thereaction mixture, which is then extracted with ethyl acetate.

The combined organic phases are washed with water, dried over sodiumsulphate and, after filtration, freed from solvent in vacuo. The residueis purified by column chromatography (eluent: petroleum ether/ethylacetate 2:1).

7.5 g (78% of theory) of methyl3-methoxy-2-[6-[4-(phenyl)-pyrimidin-2-yl]-indol-1-yl]-acrylate areobtained as an E/Z isomer mixture of melting point 85° C.

EXAMPLE 2 ##STR60## (Process (b))

A mixture of 1 g (2.9 mmol) of methyl[6-[4-(phenyl)-pyrimidin-2-yl]-indol-1-yl]-acetate and 4 g ofdimethylformamide dimethyl acetal is refluxed to the boil for 30 hours,with stirring. The mixture is allowed to cool and is concentrated, theresidue is stirred with diisopropyl ether and the solid is filtered offwith suction. The solid is washed with a little diisopropyl ether anddried.

1.1 g (95% of theory) of methyl3-dimethylamino-2-[6-[4-(phenyl)-pyrimidin-2-yl]-indol-1-yl]-acrylate isobtained as an E/Z mixture of melting point 168° C.

The compounds of the formula (I) listed in Table 2 can be preparedanalogously to Preparation Examples 1 and 2 and following the generalinstructions for processes (a), (b), (c) and (d) according to theinvention. ##STR61##

                                      TABLE 2                                     __________________________________________________________________________    Example No.                                                                          R.sup.1                                                                           R.sup.2                                                                             R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         R.sup.6                                                                         R.sup.7      R.sup.8                                                                         Melting point                         __________________________________________________________________________    3      CH.sub.3                                                                          OCH.sub.3                                                                           H H H H                                                                                            H *.sup.) 95° C.                 4      CH.sub.3                                                                          OCH.sub.3                                                                           H H H H                                                                                ##STR62##   H *.sup.) 90° C.                 5      CH.sub.3                                                                          OCH.sub.3                                                                           H H H H                                                                                ##STR63##   H *.sup.) 90° C.                 6      CH.sub.3                                                                          OCH.sub.3                                                                           H H H H                                                                                ##STR64##   H  *.sup.) 95-97° C.             7      CH.sub.3                                                                           ##STR65##                                                                          H H H H                                                                                ##STR66##   H *.sup.) 168-172° C.            __________________________________________________________________________     *.sup.) E/Z isomer mixture                                               

Preparation of the Starting Compounds EXAMPLE (IV-1) ##STR67##

A mixture of 16.0 g (59 mmol) of 6-[4-(phenyl)-pyrimidin-2-yl]-indole,17.5 g (114 mmol) of methyl bromoacetate, 23.5 g of potassium carbonateand 130 ml of acetonitrile is refluxed to the boil for 6 hours, and thecourse of the reaction is monitored by means of thin-layerchromatography. When the reaction is complete, the mixture is allowed tocool and partitioned between water and ethyl acetate, and the organicphase is dried over sodium sulphate and concentrated. The residue ispurified by column chromatography (eluent: petroleum ether/ethyl acetate1:1).

12.9 g (53% of theory) of methyl[6-[4-(phenyl)-pyrimidin-2-yl]-indol-1-yl]-acetate of melting point 111°C. are obtained.

The compounds of the formula (IV) listed in Table 3 can be obtainedanalogously to Preparation Example (IV-1).

                                      TABLE 3                                     __________________________________________________________________________     ##STR68##                            (IV)                                    Example No.                                                                          R.sup.1                                                                           R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         R.sup.6                                                                         R.sup.7      R.sup.8                                                                         Melting point                               __________________________________________________________________________    IV-2   CH.sub.3                                                                          H H H H                                                                                ##STR69##   H 159° C.                              IV-3   CH.sub.3                                                                          H H H H                                                                                ##STR70##   H 150° C.                              IV-4   CH.sub.3                                                                          H H H H                                                                                ##STR71##   H 228° C.                              IV-5   CH.sub.3                                                                          H H H H                                                                                ##STR72##   H 139° C.                              __________________________________________________________________________     ##STR73##

In an autoclave, a solution of 26.3 g (76 mmol) ofβ-dimethylamino-4-[4-(phenyl)-pyrimidin-2-yl]-2-nitrostyrene in 200 mlof tetrahydrofuran are hydrogenated for 5 hours at a hydrogen pressureof 50 bar and a temperature of 70° C., with the addition of 5 g of Raneynickel. The catalyst is separated off by filtration, the filtrate isconcentrated, and the residue is purified by column chromatography(eluent: ethyl acetate).

19.8 g (66% of theory) of 6-[4-(phenyl)-pyrimid-in-2-yl]-indole ofmelting point 160° C. are obtained.

The compounds of the formula (XI) listed in Table 4 can be obtainedanalogously to Preparation Example (XI-1).

                                      TABLE 4                                     __________________________________________________________________________     ##STR74##                          (XI)                                      Example No.                                                                          R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         R.sup.6                                                                         R.sup.7        R.sup.8                                                                         Melting point                                 __________________________________________________________________________    XI-2   H H H H                                                                                ##STR75##     H 229° C.                                XI-3   H H H H                                                                                ##STR76##     H 210° C.                                XI-4   H H H H                                                                                ##STR77##     H 206° C.                                XI-5   H H H H                                                                                ##STR78##     H Oil                                           __________________________________________________________________________     ##STR79##

A mixture of 24.0 g (111 mmol) of 4-methyl-3-nitro-benzamidinehydrochloride, 17.5 g (97 mmol) of 3-dimethylamino-acryloylbenzene and7.55 g (200 mmol) of sodium methanolate in 150 ml of ethanol is refluxedto the boil for 5 hours. After cooling, the reaction mixture is pouredinto ice-water, and the solid which has precipitated is filtered offwith suction and dried.

20.0 g (79% of theory) of2-methyl-5-(4-phenyl-pyrimidin-2-yl)-nitrobenzene of melting point 139°C. are obtained.

The compounds of the formula (XIII) listed in Table 5 can be obtainedanalogously to Preparation Example (XIII-1) and taking intoconsideration the general instructions for the processes according tothe invention.

    ______________________________________                                         ##STR80##                  (XIII)                                            Ex-                                                                           ample                                    Melting                              No.   R.sup.4                                                                             R.sup.5                                                                             R.sup.6                                                                           R.sup.7        R.sup.8                                                                           point                                ______________________________________                                        XIII-2                                                                              H     H     H                                                                                  ##STR81##     H   168° C.                       XIII-3                                                                              H     H     H                                                                                  ##STR82##     H   137° C.                       XIII-4                                                                              H     H     H                                                                                  ##STR83##     H   133° C.                       XIII-5                                                                              H     H     H                                                                                  ##STR84##     H   124° C.                       ______________________________________                                         ##STR85##

A mixture of 17.41 g (60 mmol) of2-methyl-5-[4-(phenyl)-pyrimidin-2-yl]-nitrobenzene, 52 ml ofdimethylformamide dimethyl acetal and 70 ml of dimethylformamide isrefluxed to the boil for 12 to 20 hours until the reaction is complete(thin-layer chromatographic check). The mixture is then concentratedunder greatly reduced pressure. The black-red residue, which is oily orcrystalline, is further processed without further purification.

β-Dimethylamino-4-[4-(phenyl)-pyrimidin-2-yl]-2-nitrostyrene is obtainedas an oil.

The compounds of the formula (XV) listed in Table 6 can be obtainedanalogously to Preparation Example (XV-1).

                                      TABLE 6                                     __________________________________________________________________________     ##STR86##                              (XV)                                  Example No.                                                                          R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         R.sup.6                                                                         R.sup.7      R.sup.8                                                                         R.sup.18                                                                            Melting point                             __________________________________________________________________________    XV-2   H H H H                                                                                ##STR87##   H                                                                                ##STR88##                                                                          146° C.                            XV-3   H H H H                                                                                ##STR89##   H                                                                                ##STR90##                                                                          163° C.                            XV-4   H H H H                                                                                ##STR91##   H                                                                                ##STR92##                                                                          Oil                                       XV-5   H H H H                                                                                ##STR93##   H                                                                                ##STR94##                                                                          Oil                                       __________________________________________________________________________

USE EXAMPLES

In the Use Examples which follow, the compound listed below was employedas comparison substance: ##STR95## Methyl3-methoxy-2-(2-methylphenyl)-acrylate (disclosed in EP-A 178,816).

EXAMPLE A

    ______________________________________                                        Phaedon larvae test                                                           ______________________________________                                        Solvent:    3 parts by weight of dimethylformamide                            Emulsifier: 1 part by weight of alkylaryl polyglycol                                      ether                                                             ______________________________________                                    

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage plants (Brassica oleracea) are treated with the active compoundpreparation of the desired concentration. One leaf of the treated plantsis placed in a plastic tin and infested with larvae (L₃) of the mustardbeetle (Phaedon cochleariae). After 2 to 4 days, one more leaf from thesame plant is used for each subsequent feeding.

After the desired periods of time, the destruction in % is determined.100% means that all the beetles have been killed; 0% means that none ofthe beetles have been killed.

In this test, a superior activity compared with the prior art is shown,for example, by the following compounds of the Preparation Examples:(1), (3), (4), (5) and (6).

EXAMPLE B

    ______________________________________                                        Plutella test                                                                 ______________________________________                                        Solvent:    3 parts by weight of dimethylformamide                            Emulsifier: 1 part by weight of alkylaryl polyglycol                                      ether                                                             ______________________________________                                    

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage plants (Brassica oleracea) are treated with the active compoundpreparation of the desired concentration. One leaf of the treated plantsis placed in a plastic tin and infested with larvae (L₂) of the cabbagemoth (Plutella xylostella). After 2 and 4 days, one more leaf from thesame plant is used for each subsequent feeding.

After the desired periods of time, the destruction in % is determined.100% means that all larvae have been killed; 0% means that none of thelarvae have been killed.

In this test, a superior activity compared with the prior art is shown,for example, by the following compounds of the Preparation Examples:(1), (3), (4), (5) and (6).

EXAMPLE C

    ______________________________________                                        Spodoptera test                                                               ______________________________________                                        Solvent:    3 parts by weight of dimethylformamide                            Emulsifier: l part by weight of alkylaryl polyglycol                                      ether                                                             ______________________________________                                    

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Soy bean plants (Glycine soja) are treated with the active compoundpreparation of the desired concentration. In ten replications, in eachcase one leaf of the treated plant is placed in a plastic tin and isinfested with in each case one larva (L₂) of the armyworm (Spodopterafrugiperda). After 3 days, one further leaf of the corresponding plantis used for each tin for subsequent feeding. On day 7, the larvae aretransferred to untreated artificial feed.

After the desired periods of time, the destruction in % is determined.100% means that all larvae have been killed; 0% means that none of thelarvae have been killed.

In this test, a superior activity compared with the prior art is shown,for example, by the following compounds of the Preparation Examples: (3)and (5).

EXAMPLE D

    ______________________________________                                        Nephotettix test                                                              ______________________________________                                        Solvent:    3 parts by weight of dimethylformamide                            Emulsifier: 1 part by weight of alkylaryl polyglycol                                      ether                                                             ______________________________________                                    

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Rice seedlings (Oryza sativa) are treated by being dipped in the activecompound preparation of the desired concentration and infested with thegreen rice leafhopper (Nephotettix cincticeps) while the seedlings arestill moist.

After the desired periods of time, the destruction in % is determined.100% means that all cicadas have been killed; 0% means that none of thecicadas have been killed.

In this test, a superior activity compared with the prior art is shown,for example, by the following compounds of the Preparation Examples: (3)and (5).

EXAMPLE E

    ______________________________________                                        Myzus test                                                                    ______________________________________                                        Solvent:    3 parts by weight of dimethylformamide                            Emulsifier: 1 part by weight of alkylaryl polyglycol                                      ether                                                             ______________________________________                                    

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Field bean plants (Vicia faba) which are infested with the green peachaphid (Myzus persicae) are treated by being dipped into an activecompound preparation of the desired concentration.

After the desired periods of time, the destruction in % is determined.100% means that all aphids have been killed; 0% means that none of theaphids have been killed.

In this test, a superior activity compared with the prior art is shown,for example, by the following compounds of the Preparation Examples:(1), (3), (4) and (5).

EXAMPLE F

    ______________________________________                                        Tetranychus test (OP resistant)                                               ______________________________________                                        Solvent:    3 parts by weight of dimethylformamide                            Emulsifier: 1 part by weight of alkylaryl polyglycol                                      ether                                                             ______________________________________                                    

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Bean plants (Phaseolus vulgaris) which are heavily infested with alldevelopment stages of the common spider mite or two-spotted mite(Tetranychus urticae) are treated by being dipped into the activecompound preparation of the desired concentration.

After the desired periods, the destruction in % is determined. 100%means that all the spider mites have been killed; 0% means that none ofthe spider mites have been killed.

In this test, a superior activity compared with the prior art is shown,for example, by the following compounds of the Preparation Examples: (3)and (5).

EXAMPLE G

    ______________________________________                                        Ovicidal action on egg clusters of Heliothis armigera                         (cotton bollworm)                                                             ______________________________________                                        Solvent:    3 parts by weight of dimethylformamide                            Emulsifier: 1 part by weight of alkylaryl polyglycol                                      ether                                                             ______________________________________                                    

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Egg clusters on filter paper, aged 2 days, were immersed for 30 secondsin the active compound preparations of the desired concentration and, insealed Petri dishes, deposited in the laboratory for 6 days underlong-day conditions. The criterion for assessing the action was thepercentage hatch inhibition compared with untreated egg clusters.

In this test, a superior activity compared with the prior art is shown,for example, by the following compounds of the Preparation Examples:(1), (3) and (4).

EXAMPLE H

    ______________________________________                                        Pyricularia test (rice)/protective                                            ______________________________________                                        Solvent:    12.5 parts by weight of acetone                                   Emulsifier:  0.3 part by weight of alkylaryl poly-                                        glycol ether                                                      ______________________________________                                    

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent, and theconcentrate is diluted with water and the stated amount of emulsifier tothe desired concentration.

To test for protective activity, young rice plants are sprayed with theactive compound preparation until dripping wet. After the spray coatinghas dried on, the plants are inoculated with an aqueous spore suspensionof Pyricularia oryzae. The plants are then placed in a greenhouse at100% relative atmospheric humidity and 25° C.

Evaluation of the disease infestation is carried out 4 days after theinoculation.

In this test, clearly superior activity compared with the prior art isshown, for example, by the compound of Preparation Example (6).

It is understood that the specification and examples are illustrativebut not limitative of the present invention and that other embodimentswithin the spirit and scope of the invention will suggest themselves tothose skilled in the art.

We claim:
 1. A substituted 2-[6-(pyrimidinyl)-indol-1-yl]-acrylic esterof the formula (I): ##STR96## in which R¹ represents alkyl, orrepresents optionally substituted aralkyl;R² represents dialkylamino; R³and R⁴ independently represent hydrogen, cyano, halogen or alkyl; R⁵, R⁶and R⁸ independently represent hydrogen, halogen, cyano, nitro, alkyl,alkoxy, alkylthio, halogenoalkyl, halogenoalkoxy, halogenoalkylthio,alkoxycarbonyl, alkoximinoalkyl or cycloalkyl, or represent phenyl,benzyl, phenoxy, phenylthio, benzyloxy or benzylthio each of which isunsubstituted or monosubstituted to trisubstituted in the aryl moiety byidentical or different substituents from the group consisting offluorine, chlorine, bromine, alkyl, alkoxy, alkylthio, halogenoalkyl,halogenoalkoxy and halogenoalkylthio each of which has 1 to 4 carbonatoms and if appropriate 1 to 9 identical or different halogen atoms, orrepresent pyridyl, thienyl, furyl, pyridazinyl, pyrazinyl, thiazolyl,pyridylmethyl, thienylmethyl, furylmethyl, pyridyloxy, thienyloxy,thiazolyloxy, pyridylmethyloxy, thienylmethyloxy, thienylthio,furylthio, pyridylmethylthio or thienylmethylthio each of which isoptionally monosubstituted or disubstituted in the heteroaryl moiety byidentical or different substituents selected from the group consistingof halogen, alkyl, alkoxy, alkylthio, halogenoalkyl, halogenoalkoxy andhalogenoalkylthio each of which has 1 to 4 carbon atoms and ifappropriate 1 to 9 identical or different halogen atoms; or R⁵ and R⁶together represent alkylidenedioxy or alkanediyl; and R⁷ represents##STR97## in which R⁹, R¹⁰ and R¹¹ independently represent hydrogen,halogen, cyano, nitro, alkyl, alkoxy, alkylthio, halogenoalkyl,alkoxycarbonyl, (di)alkylamino or (di)alkylaminocarbonyl, or representphenyl, benzyl, phenyloxy, phenylthio, benzyloxy or benzylthio each ofwhich is unsubstituted or monosubstituted to trisubstituted by identicalor different substituents, or represents pyrrolyl, thienyl, furyl,thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, pyrazolyl, imidazolyl,pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, triazinyl, pyrrolyloxy,thienyloxy, furyloxy, thiazolyloxy, isothiazolyloxy, oxazolyloxy,isoxazolyloxy, pyrazolyloxy, imidazolyloxy, pyridyloxy, pyrimidyloxy,pyridazinyloxy, pyrazinyloxy, pyrrolythio, thienylthio, furylthio,thiazolylthio, isothiazlylthio, oxazlylthio, isoxazolylthio,pyrazolylthio, imidazolylthio, pyridylthio, pyrimidylthio,pyridazinylthio or pyrazinylthio, each of which is unsubstituted ormonosubstituted or disubstituted by identical or different substituents,the substituents in each case being selected from the group consistingof halogen, in each case straight-chain or branched alkyl, alkoxy,alkylthio, halogenoalkyl, halogenalkoxy or halogenoalkylthio each ofwhich has 1 to 4 carbon atoms and, if appropriate, in each case 1 to 9identical or different halogen atoms, alkylcarbonylamino having 1 to 4carbon atoms in the straight-chain or branched alkyl moiety,dialkylamino or dialkylaminocarbonyl each of which has 1 to 4 carbonatoms in the respective straight-chain or branched alkyl moieties, andphenyl or benzyl each of which is unsubstituted or monosubstituted ordisubstituted by identical or different substituents independentlyselected from the group consisting of fluorine, chlorine, methyl,methoxy or phenoxy; or in which two adjacent substituents R⁹ and R¹⁰, orR¹⁰ and R¹¹, or R⁹ and R¹¹ together represent alkanediyl.
 2. Asubstituted 2-[6-(pyrimidinyl)-indol-1-yl]-acrylic ester according toclaim 1, in whichR¹ represents straight-chain or branched alkyl having 1to 4 carbon atoms, R² represents dialkylamino having in each case 1 to 4carbon atoms in the respective straight-chain or branched alkylmoieties, R³ and R⁴ are identical or different and represent hydrogen,cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl or n-,i-, s- or t-butyl, R⁵ and R⁶ are identical or different and representhydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy,methylthio, trifluoromethyl, trifluoromethoxy, difluoromethoxy,trifluoromethylthio, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl,ethoximinomethyl, methoximinoethyl, ethoximinoethyl, cyclopentyl orcyclohexyl, or R⁵ and R⁶ together represent a methylenedioxy,1,3-propanediyl or 1,4-butanediyl group, R⁷ represents one of thefollowing groups ##STR98## where R⁹ represents hydrogen, in each casestraight-chain or branched alkyl, alkoxy or alkylthio each of which has1 to 6 carbon atoms, cyclopentyl, cyclohexyl, methylamino, ethylamino,dimethylamino, diethylamino, or represents phenyl, benzyl, phenoxy,phenylthio, benzyloxy or benzylthio each of which is optionallymonosubstituted to trisubstituted by identical or differentsubstituents, or represents pyrrolyl, thienyl, furyl, thiazolyl,isothiazolyl, oxazolyl, isoxazolyl, pyrazolyl, imidazolyl, triazinyl,pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, pyridylmethyl,thienylmethyl, furylmethyl, pyridyloxy, thienyloxy, thiazolyloxy,pyridylmethyloxy, thienylmethyloxy, thienylthio, furylthio,pyridylmethylthio or thienylmethylthio each of which is optionallymonosubstituted or disubstituted by identical or different substituents,the substituents in each case being selected from the group consistingof methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy,ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio,n- or i-propylthio, n-, i-, s- or t-butylthio, methylcarbonylamino,ethylcarbonylamino, methylcarbonyl, ethylcarbonyl, n- ori-propylcarbonyl, n-, i-, s- or t-butylcarbonyl or halogenoalkyl,halogenoalkoxy or halogenoalkylthio each of which has 1 or 2 carbonatoms and 1 to 5 identical or different fluorine or chlorine atoms,dialkylamino or dialkylaminocarbonyl having 1 or 2 carbon atoms in theindividual alkyl moieties, and phenyl or benzyl each of which isunsubstituted or monosubstituted to disubstituted by identical ordifferent substituents selected from the group consisting of fluorine,chlorine, methyl, methoxy and phenoxy, and R¹⁰ and R¹¹ are identical ordifferent and represent hydrogen, straight-chain or branched alkylhaving 1 to 4 carbon atoms, chlorine, bromine, cyano, methoxycarbonyl,ethoxycarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl,methylaminocarbonyl, ethylaminocarbonyl, methoxy, ethoxy, methylthio orethylthio, or R¹⁰ and R¹¹ together represents a methylenedioxy,1,3-propanediyl or 1,4-butanediyl group, and R⁸ represents hydrogen,fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, methoxy,ethoxy, n- or i-propoxy, methylthio, trifluoromethyl, trifluoromethoxy,difluoromethoxy, trifluoromethylthio, methoxycarbonyl, ethoxycarbonyl,methoximinomethyl or ethoximinomethyl.
 3. A substituted2-[6-(pyrimidinyl)-indol-1-yl]-acrylic ester according to claim 1, inwhichR¹ represents methyl or ethyl R² represents dimethylamino ordiethylamino, R³ represents hydrogen, chlorine or methyl, R⁴ representshydrogen, chlorine or methyl, R⁵ represents hydrogen, fluorine,chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxycarbonyl orethoxycarbonyl, R⁶ represents hydrogen, fluorine, chlorine, bromine,methyl, ethyl, methoxy, ethoxy, methylthio, trifluoromethyl,methoxycarbonyl or ethoxycarbonyl, or R⁵ and R⁶ together represent amethylenedioxy, 1,3-propanediyl or 1,4-butanediyl group, R⁷ represents##STR99## where R⁹ represents hydrogen, methyl, ethyl, n- or i-propyl,n-, s-, i- or t-butyl, n- or i-amyl, n-hexyl, methoxy, ethoxy, n- ori-propoxy, methylthio, ethylthio, n- or i-propylthio, cyclohexyl,methylamino, ethylamino, dimethylamino, diethylamino, benzyl, o-, m- orp-chlorobenzyl, o-, m- or p-methylbenzyl, phenyl which is optionallymonosubstituted to trisubstitited by identical or differentsubstituents, pyridyl, thienyl, furyl, pyrimidinyl, pyridazinyl,pyrazinyl or thiazolyl, each of which is optionally monosubstituted ordisubstituted by identical or different substituents selected from thegroup consisting of fluorine, chlorine, methyl, ethyl, t-butyl, methoxy,ethoxy, methylthio, methylcarbonylamino, methylcarbonyl, ethylcarbonyl,trifluoromethyl, trifluoromethoxy, trifluoromethylthio, 1,3-propanediyl,phenyl, p-chlorophenyl, m- or p-phenoxyphenyl or benzyl, and R¹⁰ and R¹¹independently of one another represent hydrogen, methyl, ethyl,chlorine, bromine, methoxycarbonyl or ethoxycarbonyl, or R¹⁰ and R¹¹together represent a methylenedioxy, 1,3-propanediyl or 1,4-butanediylgroup, and R⁸ represents hydrogen, methyl or ethyl.
 4. A compoundaccording to claim 1, wherein such compound is methyl3-dimethylamino-2-[6-4-(phenyl)-pyrimidin-2-yl]-indol-1-yl]-acrylate ofthe formula ##STR100##
 5. A compound according to claim 1, wherein suchcompound is methyl3-dimethylamino-2-[6-[4-(4-chlorophenyl)-pyrimidin-2-yl]-indol-1-yl]-acrylateof the formula ##STR101##
 6. The method according to claim 8, whereinsuch compound ismethyl3-dimethylamino-2-[6-[4-(phenyl)-pyrimidin-2-yl]-indol-1-yl]-acrylate ormethyl3-demethylamino-2-[6-[4-(4-chlorophenyl)-pyrimidin-2-yl]-indol-1-yl]-acrylate,7. An insecticidal or fungicidal composition comprising aninsecticidally or fungicidally effective amount of a compound accordingto claim 1 and a diluent.
 8. A method of combating insects or fungiwhich comprises applying to such insects, fungi or a habitat thereof aninsecticidally or fungicidally effective amount of a compound accordingto claim 1.